C-F activation and hydrodefluorination of fluorinated alkenes at rhodium

被引：104

作者：

Noveski, D ^{[1
]}

Braun, T ^{[1
]}

Schulte, M ^{[1
]}

Neumann, B ^{[1
]}

Stammler, HG ^{[1
]}

机构：

[1] Univ Bielefeld, Fak Chem, D-33501 Bielefeld, Germany

来源：

DALTON TRANSACTIONS | 2003年 / 21期

关键词：

D O I：

10.1039/b306635e

中图分类号：

O61 [无机化学];

学科分类号：

070301 ; 081704 ;

摘要：

Reaction of [RhH(PEt3)(4)] (9) with hexafluoropropene (1) affords the C-F activation product [Rh{(Z)-CF=CF(CF3)}(PEt3)(3)] (4) as well as Et3P(F){(Z)-CF=CF(CF3)} (11). In contrast, addition of (E)-1,2,3,3,3-penta.\fluoropropene (8) to 9 yields [Rh{(E)-C(CF3)=CHF}(PEt3)(3)] (12) together with [RhF(PEt3)(3)] (6) and (Z)-1,3,3,3-tetrafluoropropene (10). Treatment of 12 with hydrogen effects the formation of 1,1,1-trifluoropropane (2) and the fluoro compounds [RhF(PEt3)(3)] (6) and cis-mer-[Rh(H)(2)F(PEt3)(3)] (7). On treatment of 6 or of a mixture of 6 and 7 with HSiPh3 the complexes [RhH(PEt3)(3)] (3) and cis-fac-[Rh(H)(2)(SiPh3)(PEt3)(3)] (13) are obtained. Both compounds are capable of the C-F activation of hexafluoropropene (1) to afford 4. The molecular structure of complex 13 has been determined by X-ray crystallography.

引用

页码：4075 / 4083

页数：9

共 106 条

[11]

Böhm VPW, 2001, ANGEW CHEM INT EDIT, V40, P3387

[12] Inertness of the aryl-F bond toward oxidative addition to osmium and rhodium complexes: Thermodynamic or kinetic origin? [J].